(1) Field of the Invention
The present invention relates to a process for producing laurolactam from cyclododecanone. More particularly, the present invention relates to a process for producing laurolactam having a high degree of purity from cyclododecanone used as a starting material.
Laurolactam is useful as a material for producing synthetic resins such as polyamide resins.
(2) Description of the Related Art
As a conventional method of producing laurolactam, a method in which cyclodododecanone, having been prepared by oxidizing cyclododecane with molecular oxygen-containing gas and dehydrogenating the resultant cyclydodecanol, is reacted, as a starting material, with a hydroxylamine mineral acid salt to prepare cyclododecanoneoxime and the resultant cyclododecanoneoxime is subjected to the Beckmann rearrangement reaction to produce the target laurolactam, is known. As another method of producing cyclododecanone, a method in which epoxycyclododecadiene is reduced with hydrogen and the resultant epoxycyclododecane is isomerized with an alkali metal salt, etc., to prepare the target cyclododecanone, is known.
In the method of producing cyclododecanone using, as a starting material, epoxycyclododecadiene, in the case where the reduction of epoxycyclododecadiene with hydrogen is incompletely carried out, the resultant epoxycyclododecane contains an impurity consisting of epoxycyclododecene and the epoxycyclododecene is converted to cyclododecenone by the isomerization reaction. The cyclododecenone is an impurity which is difficult to remove, as an impurity, from the target cyclododecanone by distillation. Also, in the case where cyclododecanol is dehydrogenated, cyclododecenone may be produced as a by-product, when the reaction conditions are inappropriate.
Further it is known that, in the reaction for isomerizing epoxycyclododecane in the presence of an alkali metal salt, undesired compounds having one or more double bonds between carbon atoms, such as cyclododecadiene, cyclododecene and cyclododecenol are produced as by-products.
Further, it is known that, in the method in which cyclododecanone, having been prepared by oxidizing cyclododecane with a molecular oxygen-containing gas and dehydrogenating the resultant cyclododecanol, is employed as a starting material for the production of laurolactam, the cyclododecanone produced by the oxidation of cyclododecane is further oxidized to produce 1,2-diketone compound and xcex1-hydroxyketone compound, and the xcex1-hydroxyketone compound is further converted to 1,2-diketone compound (cyclododecane-1,2-dione) during the dehydrogenation reaction procedure for cyclododecanol.
Where cyclododecanone is produced from a starting material consisting of epoxycyclododecadiene, the 1,2-diketone compound is not directly produced. However, when cyclododecanone is handled at a temperature of 100xc2x0 C. or more in the presence of a molecular oxygen-containing gas, the 1,2-diketone compound is produced. In this case, the 1,2-diketone compound is an impurity which is difficult to separate from cyclododecanone by distillation.
Furthermore, it is known that in a method for preparing a mixture of cyclododecanol with cyclododecanone, by oxidizing cyclododecane with a molecular oxygen-containing gas, epoxycyclododecane is produced as a by-product, and in the distillation refining procedure for isolating refined cyclododecanone from the mixture, the distilled cyclododecanone fraction contains the above-mentioned epoxycyclododecane as an impurity.
Still further, it is known that in the case where epoxycyclododecadiene is used as a starting material for the production of cyclododecanone, and subjected to an isomerization reaction thereof, a small amount of cycloundecylcarboxyaldehyde is produced as a by-product. The cycloundecylcarboxyaldehyde is an impurity which is difficult to separate from cyclododecanone by distillation.
Also, in the method of preparing a mixture of cyclododecanol with cyclododecanone by oxidizing cyclododecane with a molecular oxygen-containing gas, undecylaldehyde is produced as a by-product and is contained in refined cyclododecanone fraction obtained by distillation of the mixture.
When the aldehyde compound-containing cyclododecanone is subjected to the cyclododecanoneoxime-preparing procedure and then to the Beckmann rearrangement reaction, the aldehyde compound is converted to a corresponding amide compound and the amide compound is kept contained in the target laurolactam. The contained amide compound causes the quality of the resultant laurolactam to be decreased.
Furthermore, it is known from the disclosure of Japanese Examined Patent Publication No. 43-12153 and No. 48-10475 that, in the production of laurolactam by converting cyclododecanone to an oxime thereof and subjecting the resultant cyclododecanoneoxime to the Beckmann rearrangement reaction, if the temperature of the Beckmann rearrangement reaction is too high, the cyclododecanoneoxime is decomposed due to the poor thermal stability thereof, and the resultant laurolactam is unsatisfactory due to the low quality thereof. However, the prior art does not teach or suggest any possible influence of oxygen atom-containing organic compounds having 12 carbon atoms and cycloaliphatic unsaturated hydrocarbon compounds having 12 carbon atoms, for example, carbonyl group-containing C12-noncyclo-aliphatic and cycloaliphatic hydrocarbon compounds, epoxy group-containing C12-noncyclo-aliphatic and cycloaliphatic hydrocarbon compounds, aldehyde group-containing C12-noncyclo-aliphatic and cycloaliphatic hydrocarbon compounds, hydroxyl group-containing C12-noncyclo-aliphatic and cycloaliphatic hydrocarbon compounds contained in the starting cyclododecanone material, on the quality of the target laurolactam.
An object of the present invention is to provide a process for producing laurolactam having high quality, from cyclododecanone, with a high efficiency.
The above-mentioned object can be attained by the process of the present invention for producing laurolactam from cyclododecanone, which comprises reacting cyclododecanone with a hydroxylamine salt of a mineral acid to prepare cyclododecanoneoxime, and converting the resultant cyclododecanoneoxime to laurolactam through the Beckmann rearrangement reaction, wherein a content of each of oxygen atom-containing organic compounds having 12 carbon atoms and cycloaliphatic unsaturated hydrocarbon compounds having 12 carbon atoms, each contained, as an impurity, in cyclododecanone used as a starting material, is controlled to 1,000 ppm or less.
In the process of the present invention for producing laurolactam, the total content of the oxygen atom-containing organic compounds having 12 carbon atoms and the cycloaliphatic unsaturated hydrocarbon compounds having 12 carbon atoms and respectively contained, as impurities, in the starting cyclododecanone material, is preferably controlled to 2,000 ppm or less.
In the process of the present invention for producing laurolactam, the oxygen atom-containing organic compounds having 12 carbon atoms and contained, as impurities, in the starting cyclododecanone material may include noncyclo-hydrocarbon compounds or cycloaliphatic hydrocarbon compounds respectively having at least one carbonyl group per molecule thereof.
In the process of the present invention, for producing laurolactam, the oxygen atom-containing organic compounds having 12 carbon atoms and contained, as impurities, in the starting cyclododecanone material may include noncyclo-hydrocarbon compounds or cycloaliphatic hydrocarbon compounds respectively having at least one epoxy group per molecule thereof.
In the process of the present invention for producing laurolactam, the oxygen atom-containing organic compounds having 12 carbon atoms and contained, as impurities, in the starting cyclododecanone material may include noncyclo-hydrocarbon compounds or cycloaliphatic hydrocarbon compounds respectively having at least one aldehyde group per molecule thereof.
In the process of the present invention for producing laurolactam, the oxygen atom-containing organic compounds having 12 carbon atoms and contained, as impurities, in the starting cyclododecanone material may include noncyclo-hydrocarbon compounds or cycloaliphatic hydrocarbon compounds respectively having at least one hydroxyl group per molecule thereof.
In the process of the present invention for producing laurolactam, the content of each of the oxygen atom-containing organic compounds having 12 carbon atoms and the cycloaliphatic unsaturated hydrocarbon compounds having 12 carbon atoms, and contained, as impurities, in the starting cyclododecanone material, is preferably controlled to 500 ppm or less.
In the process of the present invention for producing laurolactam, the starting cyclododecanone material is preferably pre-treated with an aqueous solution of an alkali metal hydroxide or toluenesulfonic acid at a temperature of 70 to 230xc2x0 C.
In the process of the present invention for producing laurolactam, the starting cyclododecanone material is preferably pre-treated with a solid acid at a temperature of 70 to 230xc2x0 C.
The inventors of the present invention conducted extensive researches concerning causes of degradation in quantity of the target laurolactam when produced from a starting cyclododecanone material, and found that when the starting cyclododecanone material contained at least one member selected from oxygen atom-containing organic compounds, usually oxygen atom-containing cycloaliphatic compounds, having 12 carbon atoms and cycloaliphatic unsaturated hydrocarbon compounds having 12 carbon atoms, as an impurity, in an amount more than a limited amount, the resultant laurolactam could not exhibit, even after a distillation refining is applied thereto, satisfactory quality, for example, a satisfactory differential light transmittance (which will be referred to as LT.diff, hereinafter) of 25% or less, preferably 15% or less. Also, the inventors of the present invention further found that the target laurolactam having satisfactory quality, for example, a LT.diff of 25% or less, preferably 15% or less could be obtained by controlling the content of each of oxygen atom-containing organic compounds having 12 carbon atoms and cycloaliphatic unsaturated hydrocarbon compounds having 12 carbon atoms, contained as impurities, in the starting cyclododecanone material to a specific value or less. The process of the present invention was completed on the basis of the above-mentioned findings.
In the process of the present invention, a starting cyclododecanone material is subjected to a reaction with a hydroxylamine salt of a mineral acid to prepare cyclododecanoneoxime, and then the resultant cyclododecanoneoxime is converted to laurolactam by the Beckmann rearrangement reaction.
The starting cyclododecanone material usable for the process of the present invention can be prepared by oxidizing cyclododecane with a molecular oxygen-containing gas or by isomerizing epoxycyclododecane. In the oxidation method, cyclododecane is oxidized with oxygen gas or a molecular oxygen-containing gas in the presence of a boron compound to provide a reaction product mixture comprising cyclododecanol and cyclododecanone, the reaction product mixture is hydrolysed, the boron compound is removed from the hydrolysis product mixture, non-reacted cyclododecane is separated and recovered from the hydrolysis product mixture by distillation, and a mixture of cyclododecanol with cyclododecanone is collected from the residual fraction. The mixture is subjected to a dehydrogenation procedure to convert cyclododecanol to cyclododecanone. In this dehydrogenation procedure, a portion of the resultant cyclododecanone is occasionally further dehydrogenated to produce cyclododecenone.
Also, in the oxidation of the starting cyclododecane material with a molecular oxygen-containing gas, cyclododecane is oxidized into cyclododecanone and occasionally the resultant cyclododecanone is further oxidized into C12 1,2-diketone compounds and C12 xcex1-hydroxyketone compounds and, further occasionally, the resultant C12 xcex1-hydroxyketone compounds are dehydrogenated to produce C12 1,2-diketone compounds (cyclododecane-1,2-dione) in the dehydrogenation procedure for cyclododecanole.
In the process for producing cyclododecanone from epoxycyclododecadiene by reducing epoxycyclododecadiene with hydrogen in the presence of a platinum group metal catalyst, and isomerizing the resultant epoxycyclododecane in the presence of an alkali metal salt, to produce the target cyclododecanone, if the reduction reaction of epoxycyclododecadiene with hydrogen is incompletely conducted, epoxycyclododecene having a non-hydrogenated double bond remains in the reaction product mixture. When the epoxycyclododecane material containing epoxycyclododecene is subjected to the isomerization reaction, the resultant cyclododecanone contains cyclododecenone.
The cyclododecenone contained, as an impurity in the target cyclododecanone, is very difficult to separate and remove from the target cyclododecanone by distillation or other refining procedures. Thus, the removal of cyclododecenone causes the cost of production of the target cyclododcanone to increase. Therefore, in the production of cyclododecanone, the conditions of the production must be carefully controlled so that the production of cyclododecenone is prevented.
Also, in the isomerization of epoxycyclododecane in the presence of an alkali metal salt for the production of the target cyclododecanone, occasionally, small amounts of cyclododecene, cyclododecadiene and cyclododecenol are produced as by-products. These by-product compounds can be separated and removed from cyclododecanone by distillation. However, the yield of the target cyclododecanone decreases with increase in degree of refining. Thus, an increase in refining degree causes an economical disadvantage in the production of the target compound. The refining degree of the target compound must be controlled in consideration of the desired quality of the target cyclododecanone and the production cost thereof.
In the process for producing cyclododecanone by reducing epoxycyclododecadiene with hydrogen in the presence of a platinum group metal catalyst and isomerizing the resultant epoxycyclododecane in the presence of an alkali metal salt, the by-product, C12 1,2-diketone compounds are not directly produced. However, in the case where cyclododecanone is handled in the presence of a molecular oxygen-containing gas at a temperature of 100xc2x0 C. or more, C12 1,2-diketone compounds (cyclododecane-1,2-dione) are produced. As mentioned above, the production of the diketone compound must be carefully prevented by, for example, controlling the reaction conditions and/or the handling conditions.
Further, if the isomerization reaction of epoxycyclododecane is incompletely carried out, the non-isomerized epoxycyclododecane remains in the resultant reaction product.
As mentioned above, as the removal of the residual epoxycyclododecane from the target compound causes the resultant refined target compound to be costly, the reaction conditions for the production of the target cyclododecanone must be carefully controlled.
Further, in the isomerization of epoxycyclododecane, occasionally cycloundecanecarboxyaldehyde is produced as a by-product. The by-product cycloundecanecarboxyaldehyde is difficult to separate and remove from the target cyclododecanone by distillation, etc.
Accordingly, in the process of the present invention for producing laurolactam from a starting cyclododecanone material, it is essential that a content of each of oxygen atom-containing organic compounds, preferably oxygen atom-containing cycloaliphatic compounds, having 12 carbon atoms, and cycloaliphatic unsaturated hydrocarbon compounds having 12 carbon atoms, each contained, as an impurity, in the starting cyclododecanone material is controlled to 1,000 ppm or less, preferably 500 ppm or less, more preferably 300 ppm or less.
When the content of each impurity as mentioned above is controlled to 1,000 ppm or less, the resultant target laurolactam exhibits satisfactory quality, for example, a very low LT.diff.
The oxygen atom-containing C12 organic compounds to be controlled in the process of the present invention include, C12 non-cyclic aliphatic hydrocarbon compounds and C12 cycloaliphatic hydrocarbon compounds, each containing at least one carbonyl group per molecule thereof, for example, cyclododecadienone, cyclododecenone, 1-hydroxycyclododecane-2-one, and cyclododecane-1,2-dione.
Also, the oxygen atom-containing C12 organic compounds include non-cyclic aliphatic C12 hydrocarbon compounds and cycloaliphatic C12 hydrocarbon compounds each having at least one epoxy group per molecule thereof, for example, epoxycyclododecane, epoxycyclododecene, epoxycyclododecadiene, diepoxycyclododecane and diepoxycyclododecene.
Further, the oxygen atom-containing C12 organic compounds include C12 non-cyclic aliphatic hydrocarbon compounds and C12 cycloaliphatic hydrocarbon compounds each having at least one aldehyde group per molecule thereof, for example, undecylaldehyde and cycloundecanecarboxyaldehyde.
Furthermore, the oxygen atom-containing C12 organic compounds include non-cyclic aliphatic C12 hydrocarbon compounds and cycloaliphatic C12 hydrocarbon compounds each containing at least one hydroxyl group, for example n-dodecanol, cylododecanol, cyclododecenol, and 1-hydroxycyclododecane-2-one.
The C12 cycloaliphatic unsaturated hydrocarbon compounds to be controlled in the process of the present invention are constituted from only carbon atoms and hydrogen atoms and include, for example, cyclododecene and cyclododecadiene.
When the starting cyclododecanone material contains two or more types of the above-mentioned impurities, the total content of the impurities is preferably controlled to 2,000 ppm or less, more preferably 1,800 ppm or less, still more preferably 1,500 ppm or less, furthermore preferably 1,000 ppm or less. If the total content of the impurities is more than 2,000 ppm, even when each of the contents of impurities is 1,000 ppm or less, the resultant laurolactam may exhibit an unsatisfactory quality.
The contents of the impurities, namely, the oxygen atom-containing C12 organic compounds and the C12 cycloaliphatic unsaturated hydrocarbon compounds, contained in the starting cyclododecanone material are controlled to the desired level by, for example, the following means.
To control the contents of the non-cyclic aliphatic or cycloaliphatic C12 hydrocarbon compounds having at least one carbonyl group per molecule thereof, contained, as impurities in the starting cyclododecanone material each to 1,000 ppm or less, the reaction conditions for the isomerization of epoxycyclododecane are carefully controlled and/or the impurity-containing cyclododecanone material is brought into contact with an aqueous solution of an alkaline compound, for example, sodium hydroxide and heat-treated at a temperature of 70 to 230xc2x0 C., preferably 100 to 200xc2x0 C., while stirring the mixture, and then the resultant treatment product is refined by distillation.
To control the contents of the non-cyclic aliphatic and cycloaliphatic C12 hydrocarbon compounds having at least one epoxy group per molecule thereof to 1,000 ppm or less, the reaction conditions for production of cyclododecanone is carefully controlled and/or the cyclododecanone material containing the impurities is heat-treated with at least one member selected from a solid acids, for example, xcex3-alumina and/or silica-alumina, and ion-exchange resins, at a temperature of 70 to 230xc2x0 C., preferably 80 to 220xc2x0 C.
To control the contents of the non-cyclic aliphatic and cycloaliphatic C12 hydrocarbon compounds having at least one aldehyde group per molecule thereof to 1,000 ppm or less, the reaction conditions for the production of cyclododecanone are carefully controlled and/or the impurity-containing cyclododecanone material is heat-treated together with an alkaline substance, for example, sodium hydroxide or an acid substance, for example, toluenesulfonic acid, at a temperature of 70xc2x0 C. or more, preferably 70 to 230xc2x0 C., more preferably 80xc2x0 C. to 220xc2x0 C., and/or the impurity-containing cyclododecanone material is subjected to a reduction treatment with hydrogen in the presence of a Ru or Ni catalyst, and then the reduction-treated material is subjected to a precision distillation.
To control the contents of the non-cyclic aliphatic and cycloaliphatic C12 hydrocarbon compounds having at least hydroxyl group per molecule thereof to 1,000 ppm or less, the reaction conditions for the production of cyclododecanone are carefully controlled and/or the impurity-containing cyclododecanone material is subjected to a precision distillation, and/or the impurity-containing cyclododecanone material is heat-treated in the presence of an acid substance, for example, toluenesulfonic acid at a temperature of 70xc2x0 C. or more, preferably 70 to 230xc2x0 C., more preferably 80 to 220xc2x0 C.
To control the contents of the aliphatic unsaturated C12 hydrocarbon compounds to 1,000 ppm or less, the reaction conditions for the production of cyclododecanone are carefully controlled and/or the impurity-containing cyclododecanone material is subjected to a precision distillation.
In the case where the cyclododecanone material contains two or more types of impurities, preferably two or more of the above mentioned refining procedures are applied. However, sometimes, the contents of two or more impurities can be reduced by a single refining procedure.
The impurity content-controlled starting cyclododecanone material is reacted with a hydroxylamine salt of a mineral acid to provide cyclododecanoneoxime. The mineral acid is preferably selected from sulfuric acid and hydrochloric acid. The oxime-producing reaction is preferably carried out at a temperature of 70 to 110xc2x0 C., more preferably 90 to 100xc2x0 C. Also, the pH of the reaction mixture is preferably controlled to 1 to 10, more preferably 4 to 10, by using an aqueous alkaline solution, preferably an aqueous ammonia solution.
A solution of the resultant cyclododecanoneoxime is subjected to the Beckmann rearrangement reaction to prepare laurolactam. Preferably the Beckmann rearrangement reaction is carried out by heating the aqueous cyclododecanoneoxime solution in the presence of fuming sulfuric acid at a temperature of 90 to 130xc2x0 C., more preferably 90 to 110xc2x0 C. Cyclododecanoneoxime is in the state of a solid at room temperature and has a melting temperature of 135xc2x0 C. This compound is very unstable at the melting temperature or higher. Thus, usually cyclododecanoneoxime in the state of a solution in a solvent is subjected to the Beckmann rearrangement reaction at the above-mentioned temperature. The solvent is preferably selected from cycloaliphatic hydrocarbons, for example, cyclododecane and isopropylcyclohexane; and alkanoneoximes, for example, cyclohexanoneoximes. After the reaction, the resultant reaction mixture is neutralized with an aqueous ammonia solution, and refined by a conventional refining procedure, for example, extraction or distillation, to collect refined laurolactam.